Azo dyes and process of making same



Patented Dec. 11, 1928.

UNITED STATES PATENT OFFICE.

HERMANN WAGNER, OF SODEN-ON-THE-TAUNUS, AND HE'CNZ EICHWEDE AND ERICK FISCHER, F HOCHST-ON-THEMAIN, GERMANY, ASSIGNORS TO GRASSELLI DYE- STUFF CORPORATION, OF NEW YORK,

N. Y., A CORPORATION OF DELAWARE.

AZO DYES AND PROCESS OF MAKING SAME.

Io Drawing. Application filed December 22, 1925, Serial No. 77,097, and in Germany August 6, 1928.

CO-NH-R' wherein R represents a non-sulfonated phenyl group, R a non-sulfonated aryl residue, and X a non-sulfonated residue of the group including the benzene and naphthalene series being substituted by at least one auxochromic grou We wish it to above given formula all aryl radicles be further substituted.

Our products form in the dry state black powders being insoluble in Water and yieldmg dyeings of excellent properties as to fastness. In sohe cases the fastness of the dyeings can be considerably enhanced by an after-treatment with a copper salt.

Our products are obtainable, for instance, by diazotizing a compound of the. general formula understood that in the may one mol. of anlllne---- one mol. m-phenylenedlamine one mol. of p-phenylenediamlne 'hich is obtained by acting with one molccule of diazotlzed p-nitraniline upon the monoazo dyestutf produced by combining one molecule of diazobenzene chloride with one molecule of rn-phenylenediarnine and subsequently reducing the nitro group with sodium sulfide, are diazotized with 25-30 parts by volume of hydrochloric acid of 20 B. and 7 parts by weight of sodium nitrite. This diazo solution is run into a solution of 33 parts of the 5-chloro-Lmethyl-Q-anilide of 2-hydroxynaphthalene-3-carboxylic acid dissolved with caustic soda solution and sodium acetate in excess. The dyestuff after bemg filtered ofi' and dried, is ground in the usual manner with a substratum. The latter may also be added already in the course of the coupling process.

The dycstutl has the formula:

Qiidihydroxynaphthalone, (r-naplithol, 2- amino T hyilroxynaphthnlenc. Furthermore the 5-chlor-l'methyl-iZ-aniliile of 2-hydroxynaphtlialcne-il-carboxylic avid montioncd in the forc oing example, may be replaced by any ary lamide of 2-hydroxynaphthalcne-3-carboxylic acid.

In case of the use of 2341ihydroxynaphthalene the intermediate product has the following constitution:

N N-di' and with 2-a1ninO-T-hydroXyuuphthalene the following constitution:

R-N=N N=-N-B' 015- [k NH: @t

onmN-w 4 5 6 NH: neutralized with sodium acetate, sodium carbonate or chalk.

After the material has been wrung out, rinsed and. soaped, deep black dyeing of excellent fastncss is obtained.

The dycstuil has the formula:

(3) The material to be dyed is first padded with a solution of 28 of 5-chloro-1- methgl-Q-anilid. of Q-hydroxynaphthalene- 3-car oxylic acid, 90 cc. of caustic soda solution 22 B., 20 gr. of para. soap P. N. (ammonium ricinoleate) made up to one litre.

The material thusprepared, after being illled, 1S printed with a paste made as folows:

Dissolve:

56 gr. of the dyestuli' produced by:

1 mol. aniline in 36 cc. of hydrochloric acid B6. and 200 cc. of Water, cool with i550 gr. of ice, diazotize The prints thus obtained are distinguished by their good properties as to fastness.

The dyestuif has the formula:

ii W-GONH 2 In the foregoing Examples 2 and 3 the disazo dyestufi to be diazotized as well as the arylamide of 2-hydroxynaphthalene-3-carboxylic acid, may be varied in the manner indicated in Example 1. The dyeings and prints thus obtained are deep black and possess very good and even excellent properties as to fast-ness.

(4) 34,6 parts of the disazo dyestufi 2 mol. of p-phenylenediamine m phenylenediamine obtained by coupling mol. of diazotized p-nitraniline with 1 mol. of m-phenylenediamine and subsequently reducing the dinitro-dyestuff with sodium sulfide, are diazotized with -60 parts of hydrochloric acid of 20 B. and 14 parts of nitrite. The clear diezo solution is run into a solution of 52,6 parts of the'anilide of 2- hydroxynaphthalene-3-carboitylic acid dissolved with caustic soda solution and sodium acetate in excess. After having filtered the mixture and dried, it black wder is obtained which is combined int c usual mannor with a substratum. The coupling process may also be operated in presence of the substratum.

The dyestufi' has the formula:

The preparation of the dyestuff may be 03! ried outin an analogous manner if, instead of diamine the disazo dyestulf used in the foregoing exaniple,-tliere are used as parent products for 2 mol. of pphenyilenediamine 2 mo]. ofp-phenylenedian'zine :3. 2 mol. of p-phenylenodianiine 2 mol. of p-phenylenediamine 2 mol. of p-phenylenediamin'e 2 mol. ofp-phenylenediamine 1 2 H101! of p-phenylenediamine In case of the use of 2 mol. of p-phenylenev 1 mol. of 1.5-naphthylenediamine and 2 mol. of p-phenylenediamine q 1 mol. 'm-aminophenol, the inter- Instead of the pphenylenediamine may be used 2 mol. ofany other diaxnine such for instance. as 2-5-diamino-l-methylbenzene, 2-57 diamino-l-methoxybenzene; 2,5-diamino-1- hydroxybenzene, 2.5-diamino-l-benzoic acid, or the like; whilethe anilicle of the 2-hydroxynaphthalene 3 chrboxylic acid mentioned in the foregoing example maybe replaced by any arylamide of 2-hydroxynaphthalene- 3-carboxylie acid.

(5) 100 grams of cotton yarn are impregnated with a solution containing per litre 11,9 grams of the -5-chloro-1-methyl-2-anilide of 2-hydroxynaphthalene-3-carboxylic acid, 30 cc. of caustic soda solution of 34? B.

instance dyestufis'of the following constitution: i

1 mol. of ni-toluylencdiamine 1 mol. of l-fi-naphthylendiamine 1 niol. of m-arninodilnethylaniline V 1 incl. of tetraniethyl l-3-diaminobenaene- 1 mol. of m-amin'ophenol mol. of 2.-5-arninonaphthol.

1 mol. of 2.3-dihydroxynaphtlijalene etc and 40 cc. of sodiuinTurkey red oil. The yarn is then passed through a second bath containing per liter 4.4 grams of the following tetrazo compound neutralized with sodium acetate.

' In this manner black dyeings of excellent fastness'are obtained.

The dyestufi' has the formula (6) The material is padded with a solution of: 24,9 grams of 4-chloro-1-methoxy-2-anilide of 2-hydroxyn'aphthalene-3-carboxylie acid, cc. of caustic soda solution of .22 B.,

20 grams of para'soap P. N made up to one. litre.

the group including the'benzene and naph- The material' is then dried and printed with a paste made up as follows Dissolve: I

2 inol. o! p-phenylenedlumlne- 1 mol. ot m-toluyle'nediamlne 140 cc. of water and 24 cc. of hydrochloric acid 22 1%., cool with 150 gr. of ice, tetrazotizej with 8 gr. of nitrite dissolved in 50 cc. of water; then introduce'the whole while 18 grams of the dycstutt:

stirring into 524 gr. of tragacanth 60:1000 and add hefore'use 60 gr. of sulfate of aluminum 1:1 and 20 gr: of sodium phosphate,

about one litre.

The deep black prints thus obtained are distinguished for their very good fastness.

"The dyestuif has the formula 1 1 oo-NH 2 In the foregoing Examples 5 and 6 there inay j ust 'as in Example 4, be varied in the menner above indicated both the disazo dyestuff to be tetraz'otized and the aryl'ami'de of 2 hydroxynaphth alene- 3 carboxylic acid; thus there. are obtained .in most cases intense deep black dyeings or prin'ts'of very good properties as to fastness.

In the following claims the terms nonsulfonated phenyl group, non-sulfonated aryl residue, and non-sulfonated residue of thalene series are intended to include such I unsulfonated groups or residues, whether they are substituted by other substituents than sulfonic acid groups or not, except as 60 otherwise specifically limited in the claims.

We claim: 1. As new products the azo dyestuffs of the general formula:

- K so m-phenylenedlamine 5 1; V wherein R, represents a non-sulfonated aryl residue. 7 1

2. 'As' a new product the azo dyestufl of the most probable formula:

m-phenylenedlamlne ll l; a z being in the dry state a deepblaclr powder insoluble in water and yielding a dyeing; of excellent properties as to fa'stness 3. Material dyed with the dyestufii of claim 1.

claim 2.

5. As new products the general formula dyestufis of the 00 ma n wherein R represents a non-sulfonated phenyl group, R a non sulfonated aryl resi-' due, and X a non-sulfonated residue of the group including the benzene and naphthalene series being substituted by at least one auxochromie group.

In testimony whereof, we aflix our signatures.

'HERMANN WAGNER. HEINZ EIGHWEDE. ERICH FISCHER.

3. Material dyed with the dyestufi' of wherein R represents a non-sulfonated claim 1. phenyl roup, R a non-sulfonatcd uryl resi 4. Material dyed with the dyestufl of due, an X a non-sulfonated residue of the claim {group including the benzene and naphtha.-

5 5. As new products the dyestuffs of the ene series being substituted by at least one general formula: auxoohromic grou In testimony wl iereof, we alfix our signa- RN==N tures. N=NRN-N 10 OH HERMANN WAGNER.

HEINZ EIfi-HWEDE. oo-nn-w ERIGH FISCHER.

CERTIFICATE or CORRECTION.

'Pmm No. 1,694,568. Granted December 11. 1928, to

HERMANN WAGNER ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5. after line I), insert the following as claim 6:

6. Material dyed with the dyestuffs of claim 5.;

and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 15th day of January. A. D. 1929.

M. J. Moore, (Seal) Acting Commissioner of Patents. 

